新型空穴传输材料N,N''''-二(α-萘基)-N,N''''-二苯基-4,4''''-联萘胺的合成与光电性质

以4,4'-联萘胺为母体,以最常用的空穴传输材料N,N'-二(α-萘基)-N,N'-二苯基-4,4'-联苯胺(α-NPD)为样板,合成了新型空穴传输材料N,N'-二(α-萘基)-N,N'-二苯基-4,4'-联萘胺(α-NPN).通过核磁共振氢谱和元素分析进行了结构表征.差热分析测定其玻璃化温度(Tg)达到128 ℃.相对于α-NPD,α-NPN的吸收光谱和光致发光光谱都发生了红移.循环伏安法测定其氧化电势为1.20V,比α-NPD的1.02V稍高.该化合物可发明亮的蓝色荧光 (461 nm),积分球测定其薄膜荧光量子效率为8.5%,比α-NPD的5.5%高.初步确定α-NPN可作为有机电致发光空穴传输材料.     

N,N'-亚甲基双丙烯酰胺交联淀粉微球的合成及吸附性能

以可溶性淀粉为原料,用反相悬浮法合成了N,N'-亚甲基双丙烯酰胺交联淀粉微球ASM.最佳合成条件是可溶性淀粉2g,N,N'-亚甲基双丙烯酰胺0.2g,K2S2P8 0.04g,W/O相体积比1∶3,反应时间2h,反应温度50℃.ASM外型规则,粒度10～20 μm.探讨了成球机理,提出了交联反应主要在淀粉分子结构外围进行的推论并获得了实验支持.在25℃,ASM对Cu2 、Cr3 、Cd2 、Pb2 的饱和吸附量分别是2.75、2.20、0.88、0.77 mmol·g.HCl、ZnCl2使ASM对Cu2 的吸附量明显降低,MgCl2使吸附量略有降低.ASM的空间网状结构使金属离子容易深入其内部形成多点配位,配位吸附是ASM吸附金属离子的主要作用形式.     

橡胶硫化剂N,N'-间苯撑双马来酰亚胺的合成

研究了以乙酸做溶剂,以马来酸酐和间苯二胺为主要原料合成间苯撑双马来酰亚胺的合成方法;通过正交试验,找出了反应的优化条件;通过熔点仪、红外光谱仪、高效液相色谱仪对合成产品进行定性和定量分析.结果表明:溶剂乙酸的用量为间苯二胺质量的3倍,反应容易操作进行;催化剂与间苯二胺的摩尔比为0.05～0.3;马来酸酐与间苯二胺的摩尔比为2.1/1,在此优化条件下产物的得率为90.2%;红外光谱图与标准图谱一致,合成产物的含量为96%.     

N,N'-双(2-硫酮基苯骈噻唑基-3-甲基)-正十二胺的缓蚀性能研究

以2-巯基苯骈噻唑、甲醛和正十二胺为原料在微波辐照下合成了N,N'-双(2-硫酮基苯骈噻唑基-3-甲基)-正十二胺(DTBMDA).采用失重法和动电位极化曲线法对合成的缓蚀剂进行了缓蚀性能测试,利用扫描电镜观察了腐蚀试样表面形貌,并对其缓蚀机理进行了初步探讨.结果表明,DTBMDA能够有效抑制饱和CO2环境下N80钢的腐蚀,属于混合型缓蚀剂.DTBMDA能与金属发生多中心吸附,同时能形成致密的疏水性保护膜,从而起到缓蚀作用.     

聚二烯丙基二甲基氯化铵-丙烯酰胺-乙二醛鞣剂制备的研究

通过自由基聚合法制备了聚二烯丙基二甲基氯化铵-丙烯酰胺;以聚合物中单体转化率、鞣制后坯革的收缩温度和增厚率为考察指标,通过正交实验设计法对聚二烯丙基二甲基氯化铵-丙烯酰胺与乙二醛反应制备聚二烯丙基二甲基氯化铵-丙烯酰胺-乙二醛(PDM-AM-GL)的合成条件进行了优化.实验结果表明,PDM-AM与乙二醛反应的最优实验条件为配比是1:1.2,反应时间为5h,反应pH值为3.O,反应温度为40℃;反应后PDM-AM-GL中单体转化率为93%.将最优工艺条件下制备的聚合物应用于山羊皮鞣制工艺中,应用实验结果表明,聚合物鞣制后坯革增厚率为13.4%,△Tn为14℃;PDM-AM-GL具有一定的鞣制作用.     

联苯类三芳胺空穴传输材料的合成及其光电性能研究

以4,4'-二甲基二苯胺和3-甲基二苯胺为原料分别与4,4'-二碘联苯反应合成了N,N,N',N'-四(4-甲基苯基)-1,1'-联苯-4,4'-二胺(S-100)和N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(m-TPD),产品收率为93.3%和94.3%.以S-100和m-TPD作为空穴传输材料,以酞菁氧钛为电荷产生材料制备功能分离型有机光导器件并进行光电性能的测试,结果表明所合成化合物具有优异的空穴传输性能.     

静置水溶液聚合法合成AA/AM/AMPS高吸水性树脂

以N,N'-亚甲基双丙烯酰胺(NMBA)和聚乙烯醇(PVA)为复合交联剂,通过静置水溶液聚合法制备了丙烯酸(AA)/丙烯酰胺(AM)/2-丙烯酰胺基-2-甲基丙磺酸(AMPS)共聚高吸水性树脂.探讨了反应条件对树脂吸水性能的影响,并通过FT-IR、SEM等技术对树脂的分子结构及表面形态进行了表征分析.实验结果表明:优化条件下所合成的树脂最高吸蒸馏水倍率为1641倍.以NMBA和PVA为复合交联剂,可以优化树脂的交联网络结构,且PVA在树脂中具有双重作用.     

明胶接枝共聚丙烯酸铵-丙烯酰胺

研究了溶液聚合法制备明胶-聚(丙烯酸铵-丙烯酰胺)(G-g-PAA/PAM)可降解高吸水性树脂的方法.对明胶/单体及丙烯酸铵/丙烯酰胺质量比、丙烯酸中和度、单体浓度及N,N'-亚甲基双丙烯酰胺和过硫酸钾相对含量影响产品吸(盐)水性能的情况进行测试,从中优选出较合适的反应条件,并用红外光谱对产物进行表征.该高吸水性树脂的吸水倍率达1187g/g,吸盐水倍率选82g/g.FTIR分析表明,反应产物为明胶与丙烯铵、丙烯酰胺的接枝共聚物.     

1,1,4,4-四苯基-1,3-丁二烯衍生物的合成

以苯乙酮和溴代苯为原料,通过格氏反应先制得1,1-二苯基乙醇(1),收率为91.3%;(1)经脱水和氯甲基化得到1,1-二苯基-3-氯丙烯(2),收率为92.9%;(2)再与二苯甲酮衍生物经格氏反应制得了1,1,4,4-四苯基-1,3-丁二烯衍生物(3a)和(3b),收率高于54.0%,并对各步合成的工艺条件进行了研究.HPLC测得(3a)和(3b)质量分数均高于99.0%.通过紫外光谱、红外光谱、质谱、1H NMR和元素分析对产物的组成和结构进行了鉴定.     

2,4-己二炔-1,6-二乙基脲的合成及聚合反应

研究了一种时间-温度指示剂2,4-己二炔-1,6-二乙基脲的合成方法,用元素分析、飞行时间质谱、傅立叶变换红外光谱、激光拉曼光谱和核磁共振对其结构进行了表征,并采用光密度计、红外光谱和紫外光谱对其聚合过程进行了初步研究。结果表明,该化合物在紫外灯照射和加热两种条件下,均可以发生固相聚合反应,但在紫外灯照射下的聚合速率要比加热条件下快得多。随着聚合程度的增加,化合物的颜色逐渐由白色变为蓝色甚至黑色,并具有时间累积效应,可以作为时间-温度指示剂使用。     

硝基乙腈钾合成1,2,4-三嗪氮杂稠环化合物的研究

以2-氰基-2-羟基亚氨基乙酸乙酯（NOCNEt）为原料，在碱性条件下经氧化、水解等反应，合成了硝基乙腈钾。考察了硝基乙腈钾合成中物料比、催化剂用量、反应温度和时间对反应产率的影响，将硝基乙腈钾的总产率由28.35%提高到37.71%。使用硝基乙腈钾代替现制备的硝基乙腈，与五元氮杂环的重氮盐进行偶联、环化反应，合成了新型氮杂稠环化合物3-硝基-4-氨基-7-氰基-［1,2,4］三唑［5,1-c］［1,2,4］三嗪（AITX）。表征了产物的结构，计算了性能参数。AITX的密度为1.64 g/cm³，氮质量分数达到47.80%，生成焓为772.43 kJ/mol。     

Synthesis of LiYF4, BaYF5, and NaLaF4 optical nanocrystals

This paper reports the synthesis of high quality LiYF4, BaYF5, and NaLaF4 nanocrystals by high-temperature co-decomposition of precursors in organic solvents. Their bulk counterparts have long been used as efficient luminescent hosts for various applications including lasers, upconversion fluorescence, and quantum cutters. The particles were characterized using TEM, XRD, dynamic light scattering (DLS), and fluorescence spectrometry. Trifluoroacetic acid (CF3COOH) and the reaction temperature were crucial for the formation of NaLaF4 and LiYF4 nanoparticles. NaLaF4 was not formed without using CF3COOH, only LaF3 and NaF mixture was formed. NaLaF4 nanoparticles were obtained only when CF3COOH was added in the reaction solution and the temperature was > or =330 degrees C. For the synthesis of LiYF4,, in the absence of CF3COOH in the reaction, a mixture of YOF and LiYF4 nanoparticles was formed. Pure LiYF4 particles were obtained only until CF3COOH was added in the reaction at 340 degrees C or above. The nanoparticles were easily dispersed in organic solvents include hexane, toluene, and chloroform and formed transparent colloidal solutions. The ease of doping of these as-synthesized host nanoparticles for designed optical properties was assessed. The LiYF4, BaYF5, and NaLaF4 nanoparticles, co-doped with 20% Ytterbium (Yb) and 2% Erbium (Er), showed bright upconversion fluorescence upon 980 nm NIR excitation, confirming the high quality of as-synthesized nanoparticles. These nanoparticles are potential candidates for nano-optical devices, thin films, telecommunication, and bio-probes.     

Effect of Zn,Cu,Cr and Pb Chlorides on the Formation of Tricalcium Aluminate Trisulfate Hydrate

The effect of addition of Zn, Cu, Pb and Cr chlorides as admixtures on the hydration reaction of the system 3CaO·Al2O3-gypsum with molar ratio 1：3 was studied. Different ratios of each salt were used, namely 0.5%, 2% and 4% by weight of the solid mixture. Hydration reaction was carried out at 35℃ for various time intervals from 0.5 h to up to 7 d. Hydration rate of the system 3CaO·Al2O3-CaSO4·2H2O in absence and presence of different salts was studied via the determination of the combined water contents. X-ray diffraction analysis showed that the ettringite was the only hydration product formed in the different mixes. The hydration products were investigated by scanning electron microscopy （SEM） and thermal gravimetric analysis. The results indicated that the rate of formation of ettringite and its microstructure depend on the admixture and its dosage.     

Effects of solvent, pH, salts and resin fatty acids on the dechlorination of pentachlorophenol using magnesium-silver and magnesium-palladium bimetallic systems

The effects of pH, organic co-solvent, salts such as sodium chloride, sodium sulfate, and co-pollutants, resin and fatty acids (RFAs) on the dechlorination of pentachlorophenol (PCP) by magnesium/silver (Mg/Ag) and magnesium/palladium (Mg/Pd) systems were examined in the present investigations. Such studies provide relevant information about the applicability of bimetallic systems for remediation of raw wastewaters (such as pulp bleaching effluents) or groundwater. Removal efficiencies of 10 mg L(-1) PCP by Mg/Pd and Mg/Ag systems at the end of 1 h reaction were 93% and 78%, respectively, in the presence of acetone (1% v/v). On the other hand, the removal efficiencies were 86% and 70% for reactions conducted in alcoholic solvents (1% v/v) using Mg/Pd and Mg/Ag systems, respectively. The efficiencies of PCP removal by the two bimetallic systems could be correlated to the dipole moments of co-solvents used. The second order reaction rate constant for PCP removal by Mg/Ag system was highest (0.03 L mg(-1) min(-1)) in the absence of any pH-control mechanism. Optimum pH for the dechlorination of PCP by Mg/Pd system was found to be approximately 5.5 and >92% of the compound was removed within 15 min of reaction. Presence of chlorinated and non-chlorinated resin fatty acids (RFAs) resulted in substantial reduction in the rate and extent of PCP removal by Mg/Ag system whereas dechlorination by Mg/Pd remained unaffected. Presence of sodium sulfate or sodium chloride in the reaction phase reduced the rate and extent of PCP removal by Mg/Ag system. PCP dechlorination by Mg/Pd system was adversely impacted by the addition of sodium chloride and unaffected by the presence of sodium sulfate.     

1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的合成

以硝基甲烷为原料合成了1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷,总收率为37.8%。采用1HNMR﹑IR和MS对目标产物及中间体的结构进行了表征。在三羟甲基硝基甲烷的合成中,结合反应机理确定了氢氧化钙的用量为:n(CH3NO2)n(Ca(OH)2)=1001;通过对催化剂浓硫酸﹑三氟化硼—乙醚络合物和对甲苯磺酸的比较,得出对甲苯磺酸为中间体2,2-二甲基-5-羟甲基-5-硝基-1,3-二氧杂环己烷合成的较优催化剂;分别采用2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯和2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四对甲苯磺酸酯与NaN3反应,发现磺酸酯基易离去,叠氮化反应更易进行,收率较高;叠氮化反应的较优溶剂为DMSO。DSC分析表明,1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的分解峰温为223.46℃。     

Preparation of (Ti, Sn)O2 Nano-Composite Photocatalyst by Supercritical Fluid Dry Combination Technology

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%-30.1%) were prepared from TiCI4 and SnCl4·5H2O by using sol-gel, supercritical fluid dry and solid-phase reaction (SCFD) combination technology. Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0-4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nano-composite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (T     

钒电解液的绿色制备及其热力学分析

以分析纯V₂O₅为原料, 利用双氧水还原的方法制备钒电解液, 并对五氧化二钒的溶解机理进行了研究. 通过UV-Vis光谱分析和ICP, 对钒电解液在电解过程中钒离子的价态变化和浓度变化进行表征. 通过计算, 得到了钒电解液制备的反应焓变和吉布斯自由能变化, 结果表明: 生成硫酸氧钒的反应为放热反应, 并且该反应促进了五价钒离子的溶解. 将所制备的电解液组装成动态电池, 在电流密度为2.4 mA/cm²时, 电池的电流效率、电压效率、能量效率分别为93.6%、98.1%和91.9%, 充放电结果表明: 所制备的电解液具有很好的活性, 可以应用于钒电池.     

Structure,growth and morphology of polyphenylene sulphide

The crystallinity, particle size and morphology of polyphenylene sulphide synthesized from 1, 4-dibromobenzene and sodium sulphide have been investigated by X-ray diffraction and scanning electron microscopy. It was found that the crystallinity increased from 62 to 68% with an increase in reaction time. A reordering of crystalline structure with increase of reaction time was also noted. The particle size growth was slower as compared to the reaction rate and the distribution was very sharp. The results are compared with those for polyphenylene sulphide obtained from 1, 4-dichlorobenzene and sodium sulphide.NCL Communication No. 4504.     

对氨基苯甲酸壳聚糖酯的制备、表征及抗菌活性

壳聚糖(CTS)经氨基保护合成席夫碱,再与由对氨基苯甲酸和氯化亚砜制备的对氨基苯甲酰氯反应,产物在一定pH下氨基去保护得到了对氨基苯甲酸壳聚糖酯(ABCTSE)。产物经FT-IR、1H NMR、13C NMR进行结构表征,证实为目标产物;由元素分析得到所制得壳聚糖酯的酯化度为16.8%、40.4%;室温下,壳聚糖衍生物在蒸馏水及有机试剂中的溶解性比壳聚糖更好;产物的TG和DTG分析结果表明所制得壳聚糖酯的稳定性稍低于壳聚糖。另外,由于分子结构中两个氨基的存在,其溶于弱酸性溶液后随着形成—NH3+的增多,使其在抑菌方面有更大优势。     

新型磷系阻燃剂的合成与表征及其阻燃性能初探

以甲苯、苯基硫代膦酰二氯(DCPPS)、1,6-己二胺为原料,高锰酸钾为氧化剂,通过四步反应合成了阻燃剂双(对-N-氨基己基-苯甲酰基)苯基氧化膦(BNBPPO)。用熔点I、R、元素分析等手段对合成的BNBPPO进行了表征,并且对各步的反应条件进行了优化。通过TG初步探讨了其热稳定性。在己内酰胺聚合成尼龙6时,加入该阻燃剂。实验表明,含有7%BNBPPO的尼龙6的氧指数从24提高到29.6。